Anthracene dye and process of making same.



UNITED s rn pns PATENT OFFICE.

I FILlP KACER, OFLM ANNHEIM, GERMANY, ASSIGNOR TO BADISOHE ANILIN & SO DA FnBRlK Oli' ,LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

rin'maacnna DYE Ann rnocnssor MAKING SAME.

To all whom "it may concern:

-Be it known that I, FILIP KAEER, doctor of philoso: phy and chemist, subject of the King of Prussia,'residing at Mannheim, Germany, have invented new 5 and useful Improvements in Anthracene Dyes and Process of Making Same, Qi'which the following is a specification. i

My invention relates to the production of coloring matters of the anthracene series. i

.I have discovered that by treating 1-acetyl-amidoanthraq-uinone, or a derivative thereof which contains halogen in the anthraquinone residue, with an acid .c'hlorid such.for 'instanc'ej'as phosphorus oxychlorid, phosphorus pentachloridgl and sulfuryl chlorid, and then heating the compour obtaine d, either alone or in the presence of a condensingagent and either in the presence or not of a suitable solvent or diluting agent, 1 can obtain new coloring matters. Ii desired, the acetylation of theamido-anthraquinonebody and the treatment with the acid-chlorid can be caused to take place in oneoperation. v r

My new coloring matters possess the following general characteristics. They are extremely difiicultly soluble in organicsolvents, insoluble in caustic soda solution, and soluble in sulfuric acid yielding from red to brownred solutions. .They dissolve in alkaline hydrosulfite solution yielding yellow-brown vats which color cotton dul l brown shades. These shades, however, upon washing, become first greenish yellow and then gradually, or more quickly by treatment with dilute sodium hypochlorite solution, become orange to brown. The

dyed fiber becomes blue upon treating it with a neutral hydrosulfite solution.

I have further discovered that when preparing coloring matter from a 2-halogen-l-acetyl-amido-anthraquinonebody it is not necessary to treat such body first with an acid chlorid, but that by subjecting said body to the subsequent treatment as described above, that is to say by heating it either alone or in the presence of a condensing agent, and either in thepresence ornot of a suitable solvent, or diluting agent, it can be directly converted into coloring matter possessing the same general characteristics as above described.

The conversion into coloring matter of the 2-halogenl-acetyl-amido-anthraquinone bodies or of the compounds obtained by treating a l-acetyl-amido-anthraquinone body with acid chlorid can be caused to take place by heating such bodies for some time above their melting points; the coloring matter can be obtained from the resulting melt by extraction with nitrobenzene,

or by heating with sodium hypochlorite solution which removes impurities. The coloring matters can, however, be obtained directly in a more pure form and in Specification of Letters Patent. '7 Application filed May 9,1907. Serial Ila. 372,713-

Patented Aug. 13,1907.-

better yield by-carrying out thereaction in the presence of a solvent, or diluting agent,, such for instance as nitrobenzene and naphthalene, if desired, adding to the melt a condensing agent, such for instance assodium acetate, potassium acetate, lead acetate, aluminium chlorid,oferric chlorid, sodium carbonate, quicklirne,

lead oxid, or a mixture of sodium acetate and cuprous chlorid. H The following examples will serve to illustrate further, the nature of my invention and how it can be carried into practical effect, but my invention is not confined to these examples. The partsare by weight. I v

Example 1. Introduce ten (10') parts of l-acctylamido-anthraquinone into twenty-five (25) parts 0i boiling phosphorus oxychlorid and continue boiling the whole, in a reflux apparatus, until the solution which is at first formed is converted into a yellow crystalline mass. Treat this mass with water and filter off the compound formed and dry it, and introduce ten (1() parts thereof into one hundred and fifty (150) parts of boiling nitrobenzene. Add four (4) parts of aluminium chlorid and boil the whole for one (1) hour. When the mixture is cool, add one hundred and fifty (150) parts of alcohol and then filter 0ff,' and washwith alcohol, and dry the coloring matter which separates out. From the hydrosulfite vat it dyes cotton orange-yellow shades.

Example 2. Mix together thirteen (13) parts of l-amido-2.4-di-brom-anthraquinone, forty (40) parts of acetic anhydrid and ten (10). parts of phosphorus oxychlorid, and boil the Whole gently until thereaction is finished. Thenintroduce the mixture, slowly, while stirring, into about one hundred (100) parts oi water at a temperature oi from sixty to seventy ('70), degrees centigrade, and filter off and wash and dry the compound formed which can then be purified by recrystallization from an organic solvent, or by dissolving, it in sulfuric acid and then precipitating it. Then introduce ten (10) parts of this compound into two hundred (200) parts of boiling nitrobenzene, add two (2) parts of cuprous chlorid, and boil the whole for two (2) hours. On working .up the reaction mixture, as described in the foregoing example 1, a coloring matter is obtained which possesses properties similar to' those of the coloring matter obtained according to the said example 1.

Example 3. Boil together in a reflux apparatus for one (1) hour, on'the water bath, ten (10) parts of l-amido-anthraquinone and forty (40) parts of sulfuryl chlorid ($0 01 whereupon the amido-anthraquinone is chlorinated. Then add to the brownish yellow magma obtained ten (10) parts of acetic anhydrid and continue warming until a dark red solution is obtained. Then add fifty (50) parts of sulfuric acid and pour the whole into ice, or into water, and filteroff and dry the compound which is thereby precipitated. Introduce ten (10) parts of this compound into one hundred and fifty (150) parts of. boiling nitrobenzene. Add four (4) parts of ferric chlorid and boil the whole for one (1) hour. Then work upthe mixture as described in the foregoing example 1, whereupon a coloring matter is obtained which possesses properties similar to those of the coloring matter described in the said example 1.

Example 1,. Heat fifty parts of l-d-i-acetyl-arnido- 2.4-di-broin-anthraquinone for one (1) hour .ata temperature of two hundred and seventy (2.70) degrees Example 5. Introduce five (5) parts of anhydrous sodium acetate, one (1) part of cuprous chlorid and five (5) parts of l-acetyl-arnido-2-brom-anthraquinone into seventy-five (75) parts of boiling nitrobenzene, and boil the whole for three (3) hours. When the mixture is cool, filter-and wash the product successively with nitrobenzene, alcohol, water, dilute hydrochloric acid and water.v The product can be obtained in a finely divided condition by dissolving it in sulfuric acidand then. precipitating the solution by means of water. Example 6. Introduce one part and a half (1.5) of lead oxid, two (2) parts of anhydrous lead acetate and five (5) parts of l-di-acetyl-ainido-i ..4-di brorn-anthraquinone into seventy-five (75) parts of boilingnitrobenzene, and boil the whole for three (3) hours. When the mixture is cold, filter it and wash the product successively with nitrobonzene, alcohol, dilute acetic acid, and water. 7

Example '7. Introduce five (5) parts -of anhydrous sodium acetate, one (1) part of cuprous chlorid and five (5) parts of l-di-acetyl ainido-2.4-di-broin-anthraquinone into seventy-five (75) parts of boiling naphthalene,

and boil the whole for three (3) hours. Then treat the melt with three hundred (3G0) parts of toluene and work up the whole as described in the foregoing ex;- ample 5; The coloring matter so obtained is identical with that obtained in the'foregoing cxample'G.

Example 8. Introduce fifteen (15) parts of sodium acetate, one part and a half (1.5) of cuprous chlorid and ten' (10) parts of Lacotyl-amido-Z.4-di-broin-anthraquinone into one. hundred (100) parts of boiling nitrobenzene. Boil the whole for three (3) hours, and

work up as described in the foregoing example 5.

Now what I claim is:

1. 'lhe-process of producing coloring matter of the anthraccne series by treating a l-acctyl-amido-anthraqi1inone body with an acid chlorid and heating the compound obrained.

2. flhc process oi producing coloring matter of the anthracene series by treating a Lacetyl-amidohnthraquinonc body with an acid chlorid and heating the compound obtained with a condensing agent.

2%. 'lfhcproccss of producing coloring matter of the an thraccn'c series by treating a l-acctyl-amido-anihraquinooc body with an acid chlorid and heating the compound obtuincd with a condensing agcnt in the prcscncc of a solvent.

-i. The process of producing coloring inattcr of the, anthracenc series by, heating a 2-haiogcn-1-acciyi-aniido-anthraquinone body.

thraquinone'body in the prescnce of a solvent.

6. The process of producing coloring matter of the an thraccne series by treating l-acctyl-amido-anihruquinoniwith phosphorus ox chlorid and beating the compound so obtained with aluminium chlorid in the prcscncc of nitr benzcnc. i v

- T. The process of producing coloring matter of the anthracenc .cries by heating .l-acctyl-amido-Q-brom-anlhraprcscncc' of nitrobenzcnc,

8. .\s new articles of manufacture coloring matters of the anthraccnc series which can be obtained by treating a J-:icetyl-ainido-aurhraquiuonc body \viih an acid chlorid and hr-aiing ihc "wznpound obtained, which coloring; maitcrs are insoluble in caustic alkali solution. soluble in conccntratcd sulfuric acid ,viclding from rcd to brown-rod solutions. soluble in alkalinc h \'drosuliite solution yicldin; ycllmv-brou'n vats which dye cotton from orange to brown shades 'which shades upon ireatmcni' with neutral hydrosultiic solution become ,bluo.

0. As a new articlc' of manufacture the coloring mali iofihc anihraccnc scrios which can be obtained or ircaling l-ucctyl-amido-amhraquinonc with 1)hosphoi'usoxrchlorid and heating ihc compound so obtained wilh nluininiunr chlorid in the prcscncc of nitrolwnzcno. which coloring matter is insolublc in caustic alkali solution. soluble in conccniratcd sulfuric acid yiclding a rod solution. in alkaline lrrdrosullii'c solution yielding a ycllow-hrmrn vat which dyes cotton orungc- \'cilo\\' shades which 'shulics upon treatment Willi neutral -h \'drosui1ilc solution \r f'cuilll bluc.

in testimony whcrcol' l havc hcrcunio sol niy hand in rii'c presence of iwo subscribing \viincssi-s. I rlml' incl-Lu.

\Yitncsscs: J

' The process of producing coloring matter of the anthracene series by heating a 2-halogcn-1-acciyl-amidwan-' quinone w th sodiumacciatc amicuprous chlorid in lhc' solublc' 

